Preparation of Silver Nanocables Wrapped with Highly Cross-Linked Organic−Inorganic Hybrid Polyphosphazenes via a Hard-Template Approach

Silver/organic−inorganic hybrid poly(cyclotriphosphazene-co-4,4′-sulfonyldiphenol) (PZS) coaxial nanocables were prepared by a facile method that involves two steps: the synthesis of silver nanowires through a soft, self-seeding, polyol process followed by adhesion of the PZS nanoparticles on the surface of silver nanowires to generate a cablelike nanostructure. Both Fourier transform infrared spectroscopy and elemental analysis were used to identify the highly cross-linked structures of PZS layers. Scanning electron microscopy and transmission electron microscopy results indicated that the nanocables had a core ca. 80 nm in diameter and a surrounding sheath with controllable thickness. Thermogravimetric analysis showed that the silver/PZS nanocables were stable up to 440 °C under air atmosphere. This approach could be extended to other metal nanocables wrapped with highly cross-linked organic−inorganic hybrid polyphosphazenes

Facile Template-Free Fabrication of Aluminum-Organophosphorus Hybrid Nanorods: Formation Mechanism and Enhanced Luminescence Property

Recently, much effort has been directed toward fabrication of metal-organophosphorus hybrids with microporous, fibered, layered, and open structures to obtain desired mechanical, optical, electric, and catalytic properties. In this work, aluminum–phosphorus hybrid nanorods (<b>APHNRs</b>) with regular morphology were prepared by a template-free hydrothermal reaction of aluminum hydroxide with diphenylphosphinic acid (DPPA). Structure characterization of <b>APHNRs</b> by Fourier transform infrared spectroscopy, laser Raman spectroscopy, and X-ray diffraction demonstrate a structure with aluminophosphate main chains and phenyl pendant groups, which enable self-assembly into nanorods. The reaction conditions and the structures of phosphinic acids appear to have a significant impact on the morphology and size of nanorods. Moreover, the evolution of morphology and structure assembly during the forming process of <b>APHNRs</b>, as monitored by SEM and XRD, reveal a decomposition-assembly propagation process where the driving force of assembly is attributed to π–π stacking interactions between phenyl pendant groups. <b>APHNRs</b> show a significant increase in light emission relative to pure DPPA due to their compact structure resulting from the π–π stacking interaction. Detailed investigation revealed that photoluminescence was remarkably amplified by enhancing the compactness of <b>APHNRs</b>

Ultralong-Term Durable Anticorrosive Coatings by Integration of Double-Layered Transfer Self-Healing Ability, Fe Ion-Responsive Ability, and Active/Passive Functional Partitioning

The application of self-healing polymers in corrosion protection is often limited by their slow and nonautonomous healing ability and poor long-term durability. In this paper, we propose a double-layered transfer self-healing coating constructed by soft and rigid polymer layers. The soft polymer has a fast self-healing rate of 10 min to repair, which was found to accelerate the self-healing of the upper rigid layer. The rigid polymer provided relatively high barrier ability while preserving certain self-healing ability owing to the shear-thinning effect. In this way, the double-layered coating combined rapid self-healing (∼1 h) and high impedance modulus |Z|f‑0.01 Hz of 2.58 × 1010 Ω·cm2. Furthermore, the introduction of pyridine groups in B-PEA and polyacrylate-grafted-polydimethylsiloxane (PEA-g-PDMS) induced the Fe ion-responsive ability and shortened the self-healing time to 40 min (100 ppm Fe). Finally, barrier and anode sacrificed layers were introduced to produce multilayered architecture with active/passive anticorrosion performance. In the presence of scratches, the |Z|f‑0.01 Hz can be preserved at 1.03 × 1010 Ω·cm2 after 200 days. The created anticorrosive coating technology combines long-term durability with room temperature autonomous rapid self-healing capability, providing a broad prospect for anticorrosive applications

Gas–Liquid Reactions to Synthesize Positively Charged Fe₃O₄ Nanoparticles on Polyurethane Sponge for Stable and Recyclable Adsorbents for the Removal of Phosphate from Water

The application of most current phosphate adsorbents is limited by their high cost, low removal capacity, difficulty of recovery, and short lifetime. In this study, we developed a gas–liquid reaction assisted by a coordination method to prepare highly positively charged ferroferric oxide (Fe3O4) nanoparticles loaded on polyurethane sponge. It was found that the gas–liquid reaction drastically decreases the size and increases the loading capacity of Fe3O4 nanoparticles as compared with the conventional liquid method. Further, the use of trimethylamine vapor induced the coordination of Fe3+, facilitated the formation of free Cl ions, and inhibited the hydrolysis of Fe–Cl bonds, thus greatly decreasing the amount of hydroxyl groups and increasing the surface positive charge on Fe3O4 nanoparticles. As a result, the Fe3O4 nanoparticles in this study have a saturated PO43– adsorption capacity of 229.8 mg·g–1, which was appreciably higher than that of conventional Fe3O4 adsorbents (57.8 mg·g–1). Our study further revealed that the introduction of a thin layer of polyurethane coating on the surface of Fe3O4 nanoparticle-composited adsorbents could drastically improve their stability while preserving the adsorption capacity under the impact of water (500 rpm stirring for 72 h). The composited adsorbents also preserve the adsorption capacity after recycling three times. Finally, the adsorption experiment on real river wastewater indicated that the composited adsorbents enable the decrease of phosphate concentration from 0.6 to 0.02 ppm, reflecting the application potential for relieving phosphate pollution in neutral waters

Thiol-Functionalized Hybridized Porous Polymer on Polyurethane Foam for Recyclable Adsorption of Multiple Ions

The pollutants in the excessive discharge of industrial and daily wastewater, which contain multiple metal ions and anions, will cause irreversible damage to the environment and human body. However, current adsorbents only possess adsorption ability toward single type of ion, thus greatly limiting the adsorption efficiency. In this work, we prepared thiol functionalized poly(di(4-vinylpyridine)-zinc chloride-co-divinylbenzene) (Poly(ZnVP2-co-DVB)-SH) with a semicoordinated structure, coordinated/covalent hybridized skeletons, and thiol functional groups via a coordination-polymerization method. On the basis of the radical polymerization, we developed an in situ and facile method to graft Poly(ZnVP2-co-DVB)-SH on polyurethane foam (PU). Due to the semicoordinated structure and thiol groups, the composited foam demonstrated the adsorption capacity toward different ions (Pb2+, Cu2+, and PO43–). The saturated adsorption capacity of the composited foam toward Pb2+, Cu2+, and PO43– can reach to at 228.4, 91.3, and 160.1 mg·g–1, respectively. The adsorption capacity of PO43– is appreciably higher than that of the phosphate adsorbents except the biochars. Adsorption mechanism investigation reveals that the adsorption ability toward multiple ions is arising from multiple interaction, including the coordination centers exchange, thiol-lead reaction, anion exchange, and direct reaction between pyridine-phosphate. The foam can be recycled at least three times. Besides, it shows removal percentages for Pb2+, Cu2+, and PO43– in real urban wastewater. Overall, the modified foam demonstrates a high and multifunctional performance, which is potentially used for water treatment

Copper-Catalyzed Aerobic Oxidation for the Amination of Benzoxazole Under Air

<div><p></p><p>A practical copper-catalyzed aerobic oxidation for the amination of benzoxazole with secondary amine has been discovered. This reaction has proved to be effective to a variety of amines with lower catalyst loading amount, and only oxygen in air is required to facilitate this transformation. A copper-catalyzed/amine-induced ring opening of the benzoxazole and recyclization mechanism was also proposed.</p> </div

Vanadium-Containing Chloroperoxidase-Catalyzed Versatile Valorization of Phenols and Phenolic Acids

The downstream product transformation of lignin depolymerization is of great interest in the production of high-value aromatic chemicals. However, this transformation is often impeded by chemical oxidation under harsh reaction conditions. In this study, we demonstrate that hypohalites generated in situ by the vanadium-containing chloroperoxidase from Curvularia inaequalis (CiVCPO) can halogenate various electron-rich and electron-poor phenol and phenolic acid substrates. Specifically, CiVCPO enabled decarboxylative halogenation, deformylative halogenation, halogenation, and direct oxidation reactions. The versatile transformation routes for the valorization of phenolic compounds showed up to 99% conversion and 99% selectivity, with a turnover number of 60,700 and a turnover frequency of 60 s–1 for CiVCPO. This study potentially expands the biocatalytic toolbox for lignin valorization

Efficient Osteogenic Activity of PEEK Surfaces Achieved by Femtosecond Laser–Hydroxylation

Poly(etheretherketone) (PEEK) is regarded as an attractive orthopedic material because of its good biocompatibility and mechanical properties similar to natural bone. The efficient activation methods for the surfaces of PEEK matrix materials have become a hot research topic. In this study, a method using a femtosecond laser (FSL) followed by hydroxylation was developed to achieve efficient bioactivity. It produces microstructures, amorphous carbon, and grafted −OH groups on the PEEK surface to enhance hydrophilicity and surface energy. Both experimental and simulation results show that our modification leads to a superior ability to induce apatite deposition on the PEEK surface. The results also demonstrate that efficient grafting of C–OH through FSL–hydroxylation can effectively enhance cell proliferation and osteogenic differentiation compared to other modifications, thus improving osteogenic activity. Overall, FSL hydroxylation treatment is proved to be a simple, efficient, and environmentally friendly modification method for PEEK activation. It could expand the applications of PEEK in orthopedics, as well as promote the surface modification and structural design of other polymeric biomaterials to enhance bioactivity

Efficient Osteogenic Activity of PEEK Surfaces Achieved by Femtosecond Laser–Hydroxylation

Poly(etheretherketone) (PEEK) is regarded as an attractive orthopedic material because of its good biocompatibility and mechanical properties similar to natural bone. The efficient activation methods for the surfaces of PEEK matrix materials have become a hot research topic. In this study, a method using a femtosecond laser (FSL) followed by hydroxylation was developed to achieve efficient bioactivity. It produces microstructures, amorphous carbon, and grafted −OH groups on the PEEK surface to enhance hydrophilicity and surface energy. Both experimental and simulation results show that our modification leads to a superior ability to induce apatite deposition on the PEEK surface. The results also demonstrate that efficient grafting of C–OH through FSL–hydroxylation can effectively enhance cell proliferation and osteogenic differentiation compared to other modifications, thus improving osteogenic activity. Overall, FSL hydroxylation treatment is proved to be a simple, efficient, and environmentally friendly modification method for PEEK activation. It could expand the applications of PEEK in orthopedics, as well as promote the surface modification and structural design of other polymeric biomaterials to enhance bioactivity

Nucleation Domains in Biomineralization: Biomolecular Sequence and Conformational Features

Biomolecules play a vital role in the regulation of biomineralization. However, the characteristics of practical nucleation domains are still sketchy. Herein, the effects of the representative biomolecular sequence and conformations on calcium phosphate (Ca-P) nucleation and mineralization are investigated. The results of computer simulations and experiments prove that the line in the arrangement of dual acidic/essential amino acids with a single interval (Bc (Basic) -N (Neutral) -Bc-N-Ac (Acidic)- NN-Ac-N) is most conducive to the nucleation. 2α-helix conformation can best induce Ca-P ion cluster formation and nucleation. “Ac- × × × -Bc” sequences with α-helix are found to be the features of efficient nucleation domains, in which process, molecular recognition plays a non-negligible role. It further indicates that the sequence determines the potential of nucleation/mineralization of biomolecules, and conformation determines the ability of that during functional execution. The findings will guide the synthesis of biomimetic mineralized materials with improved performance for bone repair